TWI435947B - Preparation of metal oxide thin film via cyclic cvd or ald - Google Patents

Description

Method for preparing metal oxide film by cyclic CVD or ALD Related applications cited

This patent application claims priority to US Provisional Patent Application Serial No. 61/044,270, filed on Apr. 11, 2008.

This invention relates to the preparation of metal oxide films using cyclic CVD or ALD.

As one of the promising capacitor materials for next-generation dynamic random access memory (DRAM) devices, high dielectric constant (high-k) films such as SrTiO ₃ (STO) and Ba(Sr)TiO ₃ (BST) have been widely used. the study. In view of this use, it is necessary to perform a very uniform deposition of film thickness and composition on a three-dimensional (3-D) capacitor structure.

In recent years, various source materials have been used for the study of atomic layer deposition (ALD) processes to meet these requirements. ALD is one of the most promising technologies due to its unique self-limiting deposition mechanism. With a layer-by-layer film deposition process, ALD typically exhibits low deposition temperatures, excellent step coverage over high aspect ratio features, good thickness uniformity, and precise thickness control.

Plasma enhanced ALD (PEALD) has also evolved due to advantages such as higher deposition rates and lower deposition temperatures while maintaining the advantages of ALD.

As the precursor material, for example, bis(2,2,6,6-tetramethyl-3,5-heptadioic acid) can be used, that is, (Sr(thd) ₂ ) as a precursor of Sr. TTIP (Ti-tetraisopropyl oxide) is used as a precursor of Ti, and O ₃ , O ₂ plasma or water vapor is used as an oxidant to deposit an STO film. Especially for the precursor of Sr, although the precursors of Sr(thd) ₂ and some other Sr have been extensively studied, these precursors are still limited, such as low vapor pressure and low temperature thermal decomposition.

Therefore, there is still a need to develop a suitable precursor of a Group 2 or Group 4 metal and a corresponding deposition process, and it is particularly important to find a complex of a Group 2 and Group 4 metal having a similar ligand, thereby Their physical and chemical properties are consistent, such as melting point, solubility, evaporation behavior, and reactivity with respect to semi-product type semiconductor surfaces. Therefore, the complex of the Group 2 and Group 4 metals can be dissolved in a solvent and transferred to the reaction chamber to deposit a multi-component metal oxide film for DRAM.

The present invention is a cyclic deposition method for preparing a metal oxide film on a substrate, comprising the steps of: introducing a metal ketoiminate into a deposition chamber, and depositing a metal ketimine salt on the heated substrate; Purging the deposition chamber to remove unreacted metal ketimine salt and any by-products; directing the oxygen-containing source to the heated substrate; purging the deposition chamber to remove any by-products; repeating the cyclic deposition process until formation A film of the desired thickness.

The present invention describes a method of preparing a metal or multi-component metal oxide film, such as hafnium oxide, titanium oxide or barium titanate, which film can be used to produce semiconductor devices. The metal or multi-component metal oxide film provided by the method disclosed by the present invention has a dielectric constant that is significantly higher than that of a conventional thermal ceria, tantalum nitride or zirconium/niobium oxide dielectric material.

The present invention uses a cyclic chemical vapor deposition (CCVD) or atomic layer deposition (ALD) technique to deposit a metal oxide film. In a particular embodiment, the metal oxide film is deposited by a plasma enhanced ALD (PEALD) or plasma enhanced CCVD (PECCVD) process. In this embodiment, the deposition temperature can be relatively low, for example 200-600 ° C, to control specific specifications for film properties required to achieve DRAM or other semiconductor applications. The disclosed method utilizes a metal ketimide salt precursor and an oxygen source to form a metal oxide film.

A typical method is described below:

Step 1: contacting the vapor of the metal ketimine salt precursor with the heated substrate to chemically adsorb the precursor on the heated substrate;

Step 2: remove any unabsorbed metal ketimine salt precursor and any by-products;

Step 3: introducing an oxygen source onto the heated substrate to react with the adsorbed metal ketimide precursor; and

Step 4: Remove any unreacted oxygen source and by-products.

In one embodiment, the ketimine salt precursor is selected from the group consisting of the following structures:

Among them, M is a Group 2 divalent metal including calcium, magnesium, strontium, and barium. A series of organic groups may be utilized, for example wherein R ^{1 is} selected from an alkyl group having from 1 to 10 carbon atoms and preferably from 1 to 6 carbon atoms, a fluoroalkyl group, an alicyclic group, and having 6 to 12 carbon atoms a group consisting of aryl groups; R ^{2 is} selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms and preferably having 1 to 6 carbon atoms, an alkoxy group, an alicyclic group, and an aromatic having 6 to 12 carbon atoms. a group consisting of a group; R ^{3 is} selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and preferably 1 to 6 carbon atoms, a fluoroalkyl group, an alicyclic group, and an aryl group having 6 to 12 carbon atoms. R ⁴ is a C _2-3 linear or branched alkyl bridge with or without a palmitic carbon atom, thereby forming a five- or six-membered coordination ring with the metal center. Exemplary alkyl bridges include, but are not limited to, -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -, -CH(Me)CH ₂ -, -CH ₂ CH(Me)-; R ^5-6 independently Is selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and preferably 1 to 6 carbon atoms, a fluoroalkyl group, an alicyclic group, and an aryl group having 6 to 12 carbon atoms, and they are capable of linking A ring containing a carbon, oxygen or nitrogen atom is formed. The metal ketimine salt of structure A is preferably selected from Sr{ ^t BuC(O)CHC(NCH ₂ CH ₂ N Me ₂ )Me} ₂ full Sr{ ^t BuC(O)CHC(NCH ₂ CH ₂ NEt ₂ )Me} ₂ , a group consisting of Sy{ ^t BuC(O)CHC(NCH(Me)CH ₂ NMe ₂ )Me} ₂ and Sr{ ^t BuC(O)CHC(NCH(Me)CH ₂ NEt ₂ )Me} ₂ .

In another embodiment, the ketimine salt precursor is selected from the group consisting of the following structures: Wherein M is a Group 4 tetravalent metal including titanium, zirconium or hafnium. A series of organic groups may be utilized, for example wherein R ^{7 is} selected from alkyl, fluoroalkyl, alicyclic and having 6 to 12 carbon atoms having from 1 to 10 carbon atoms and preferably from 1 to 6 carbon atoms Group of aryl groups; R ^{8-9 is} selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms and preferably having 1 to 6 carbon atoms, an alkoxy group, an alicyclic group, and having 6 to 12 carbon atoms a group consisting of aryl groups; R ¹⁰ is a C _2-3 linear or branched alkyl bridge with or without a palmitic carbon atom, and a five- or six-membered coordination ring with a metal center. Exemplary alkyl bridges include, but are not limited to, -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -, -CH(Me)CH ₂ -, -CH ₂ CH(Me)-.

The disclosed methods can include one or more purge gases. In the step of removing unreacted reactants and/or by-products, the purge gas used is an inert gas that does not react with the precursor, and may preferably be selected from the group consisting of Ar, N ₂ , He, and mixtures thereof. gas. Depending on the deposition method, a purge gas, such as Ar, is delivered to the reactor, for example to provide a gas at a flow rate of about 10-2000 sccm for about 0.1-1000 seconds, thereby removing unreacted materials and any by-products still present in the reaction chamber.

The substrate temperature within the reactor, i.e., within the deposition chamber, may preferably be less than about 600 ° C, and more preferably less than about 500 ° C, while the process pressure may preferably be from about 0.01 Torr to about 100 Torr, and more preferably about 0.1 Torr - About 5 Torr.

The oxygen source in step 3 may be an oxygen-containing source selected from the group consisting of oxygen, oxygen plasma, water, water plasma, ozone, nitrous oxide, and mixtures thereof.

In each step of transporting the precursor and the oxygen source gas, the stoichiometric composition of the resulting metal oxide film can be varied by varying their delivery duration. For a multi-component metal oxide film, in step 1, a ketimine salt precursor selected from the structure "A" or "B" can be introduced alternately into the reaction chamber.

A direct liquid transport method can be employed by dissolving the ketimine salt in a suitable solvent or solvent mixture to prepare a solution having a molar concentration of from 0.01 to 2 M depending on the solvent or solvent mixture used. The solvent used in the present invention may include any compatible solvent or a mixture thereof, and includes aliphatic hydrocarbons, aromatic hydrocarbons, linear or cyclic ethers, esters, nitriles, alcohols, amines, polyamines, and organic decylamine compounds, preferably. A solvent having a high boiling point such as 1,3,5-trimethylbenzene (boiling point 164 ° C) or N-methyl-2-pyrrolidone (boiling point 202 ° C), and more preferably a polar solvent such as tetrahydrofuran (THF) or N a solvent mixture of methylpyrrolidone (NMP) and a non-polar solvent such as dodecane.

The plasma generation process includes a direct plasma generation process that produces plasma directly within the reactor, or a plasma generated outside of the reactor and delivered to a remote plasma generation process within the reactor.

In order to form a ternary metal oxide film, the present invention also devises a cyclic deposition process in which a plurality of precursors are sequentially introduced into a deposition chamber, evaporated, and deposited on a substrate under conditions in which the ternary metal oxide film is formed. on.

The present invention also contemplates that the obtained metal oxide film can be exposed to a plasma for treatment to densify the obtained multi-component metal oxide film.

SUMMARY OF THE INVENTION The present invention is a method of efficiently depositing a metal oxide or multi-component metal oxide film which can be used in a semiconductor device structure. With the present invention, it is possible to selectively form a metal oxide film using an atomic layer deposition ALD or CCVD method depending on process conditions.

ALD growth is performed by alternately exposing the surface of the substrate to different precursors. It differs from CVD in that the gas phase precursors are strictly separated from each other. Under ideal ALD process conditions, the growth of the film is carried out by self-limiting controlled surface reactions. If the surface is saturated, the pulse length of each precursor and the deposition temperature have no effect on the growth rate.

The CCVD process can be performed in a higher temperature range than the ALD process in which the precursor is decomposed. CCVD is distinguished from conventional CVD in terms of the separation of precursors. In CCVD, each precursor is introduced in order and completely in a separate manner, but in conventional CVD, all of the reactant precursors are introduced into the reactor and are allowed to interact with each other in the gas phase. reaction. A common feature of CCVD and conventional CVD is that both involve thermal decomposition of the precursor.

The present invention is also a method for efficiently fabricating a metal oxide film by using a plasma enhanced ALD_(PEALD) technique to fabricate a semiconductor device structure. Metal oxide films can be prepared by CVD and typical thermal ALD methods, however, deposition speed can be improved by PEALD, and PEALD is known to improve film properties and broaden the process window.

Example 1

This example describes the use of a ketimine salt precursor Sr{ ^t BuC(O)CHC(NCH ₂ CH ₂ NMe ₂ )Me} ₂ and O ₂ in Sr dissolved in 1,3,5-trimethylbenzene. Slurry to deposit CCVD of SrO. The deposition temperature ranged from 200 to 400 ° C and the Sr precursor was delivered using a DLI (direct liquid injector) with an evaporator. The pressure in the deposition chamber ranges from about 1.5 Torr, depending on the gas flow rate. The metal container contains a Sr precursor dissolved in a liquid (1,3,5-trimethylbenzene), the sealing tube side of which is connected to the injection valve of the DLI system, and the pressurized N ₂ (~30 psig) is Attached to the other side of the metal container to propel the liquid. One cycle of CCVD for SrO consists of five steps.

Injection of a 0.1 M Sr precursor solution in 1.1,3,5-trimethylbenzene: opening the injection valve for a few milliseconds will provide a vapor containing the Sr precursor in the evaporator;

2. Sr pulse: introducing the vapor of the Sr precursor into the deposition chamber; and chemically adsorbing the Sr precursor on the heated substrate;

3. Ar purge: use Ar purge to remove any unadsorbed Sr precursors;

4. O ₂ plasma pulse: introducing O ₂ into the deposition chamber while providing radio frequency (RF) power (in this case 50 watts (W)) to react with the Sr precursor adsorbed on the heated substrate;

5. Ar purge: Any unreacted O ₂ and by-products were removed using an Ar purge.

In this example, an SrO film was obtained, which indicates that the deposition temperature has a certain influence on the SrO film. The injection time is 2 milliseconds, the pulse time of Sr is 5 seconds, the Ar purge time after the Sr pulse is 10 seconds, the O ₂ plasma pulse time is 3 seconds, and the Ar purge time after the O ₂ plasma pulse is 10 second. Repeat the cycle 150 times.

The results are shown in Figure 3, where the ALD process window is as high as ~320 °C.

Example 2

In this example, the SrO film was deposited via the following process conditions: 0.1 M Sr precursor in the 1,3,5-trimethylbenzene-Sr{ ^t BuC(O)CHC(NCH ₂ CH ₂ NMe ₂ ) The injection time of the Me} ₂ solution is 2 milliseconds, the pulse time of the Sr precursor is 5 seconds, the Ar purge time after the Sr pulse is 10 seconds, the O ₂ plasma pulse time is 3 seconds, and after the O ₂ plasma pulse The Ar purge time is 10 seconds. The wafer temperature was 250 °C. The experiment was repeated at 50, 150, 250, 300 and 600 cycles. The results are shown in Figure 4, which shows a linear relationship between film thickness and number of cycles, which is a feature of the ALD process.

Example 3

In this example, the SrO film was deposited via the following process conditions: 0.1 M Sr precursor in the 1,3,5-trimethylbenzene-Sr{ ^t BuC(O)CHC(NCH ₂ CH ₂ NMe ₂ ) The injection time of the Me} ₂ solution was 2 milliseconds, the Ar purge time after the Sr precursor pulse was 10 seconds, the O ₂ plasma pulse time was 3 seconds, and the Ar purge time after the O ₂ plasma pulse was 10 seconds. The wafer temperature was 250 °C. The Sr pulse time varies between 1 and 7 seconds. The results are shown in Figure 5, which shows the Sr pulse saturation curve at about 5 seconds, which means a typical self-limiting ALD process under these process conditions.

Example 4

This example describes the deposition of a ketimine salt precursor Sr{ ^t BuC(O)CHC(NCH ₂ CH ₂ NMe ₂ )Me} ₂ and ozone dissolved in Sr of 1,3,5-trimethylbenzene. ALD or CCVD of SrO. The deposition temperature ranged from 200 to 425 ° C and the Sr precursor was delivered using a DLI (direct liquid injector) with an evaporator. The pressure in the deposition chamber ranges from about 1.5 Torr, depending on the gas flow rate. The metal container contains a Sr precursor dissolved in a liquid (1,3,5-trimethylbenzene), the sealing tube side of which is connected to the injection valve of the DLI system, and the pressurized N ₂ (~30 psig) is Attached to the other side of the metal container to propel the liquid. One cycle of the SrO CCVD process consists of five steps.

Injection of a 0.1 M Sr precursor solution in 1.1,3,5-trimethylbenzene: opening the injection valve for a few milliseconds will provide a vapor containing the Sr precursor in the evaporator;

2. Sr pulse: introducing the vapor of the Sr precursor into the deposition chamber; and chemically adsorbing the Sr precursor on the heated substrate;

3. Ar purge: use Ar purge to remove any unadsorbed Sr precursors;

4. Ozone pulse: introducing ozone into the deposition chamber;

5. Ar purge: Any unreacted ozone and any by-products were removed using an Ar purge.

In this example, an SrO film was obtained, which indicates that the deposition temperature has a certain influence on the deposition rate of the obtained SrO film. The injection time was 2 milliseconds, the Sr pulse time was 5 seconds, the Ar purge time was 10 seconds after the Sr pulse, the ozone pulse time was 5 seconds, and the Ar purge time after the ozone pulse was 10 seconds.

The results are shown in Figure 6, where the ALD process window is as high as ~340 °C.

Example 5

This example describes the use of a Srketimine salt precursor Sr{ ^t BuC(O)CHC(NCH(Me)CH ₂ NMe ₂ )Me} ₂ in 10% by weight of THF dissolved in dodecane. And ozone to deposit SrO in ALD or CCVD processes. The deposition temperature ranged from 200 to 425 ° C and the Sr precursor was delivered using a commercially available DLI (Direct Liquid Syringe). The pressure in the deposition chamber ranges from about 1.5 Torr, depending on the gas flow rate. The metal vessel was filled with Sr precursor in 10% (wt) THF dissolved in dodecane, the sealing tube side was attached to the injection valve of the DLI system, and pressurized N ₂ (~30 psig) was attached The other side of the metal container is used to propel the liquid. In this case, the injection valve is normally open, and the liquid mixture of the Sr precursor and the above solvent is evaporated by a nozzle (atomizer). The Ar carrier gas contributes to the evaporation behavior. One cycle of SrO's ALD or CCVD process consists of four steps.

1. Injecting 0.1 M Sr{ ^t BuC(O)CHC(NCH(Me)CH ₂ NMe ₂ )Me} ₂ solution in 10% (wt) THF in dodecane to vaporize the Sr precursor To the deposition chamber; and chemically adsorbing the Sr precursor on the heated substrate;

2. Ar purge: use Ar purge to remove any unadsorbed Sr precursors;

3. Ozone pulse: introducing ozone into the deposition chamber;

4. Ar purge: Any unreacted ozone and any by-products were removed using an Ar purge.

In this example, an SrO film was obtained, and it was shown that the deposition temperature had a certain influence on the thickness of the obtained SrO film. The injection time of the Sr pulse time was 5 seconds, the Ar purge time after the Sr pulse was 5 seconds, the ozone pulse time was 5 seconds, and the Ar purge time after the ozone pulse was 5 seconds.

The results are shown in Figure 7, where the ALD process window is as high as ~320 °C.

Example 6

In this embodiment, the direct liquid injection evaporator is performed when the Sr precursor -Sr{ ^t BuC(O)CHC(NCH ₂ CH ₂ NMe ₂ )Me} ₂ dissolved in the solvent is evaporated by a heated syringe. monitor. In this case, the syringe was heated to 185 ° C, the carrier gas was helium at a flow rate of 500 sccm, and the mass flow rate of the precursor-solvent was 1 g/min. The pressure monitor is located in front of the syringe and is located directly in the carrier gas stream.

The results in Figure 8 show that a combination of 10% (wt) THF in dodecane exhibits a very stable back pressure over a ~3 hour run time. Conversely, the same concentration of the ruthenium precursor dissolved in 1,3,5-trimethylbenzene exhibits a continuously increasing counter pressure as the other precursor streams pass through the injector system. The synergistic effect of the higher boiling point of the solvent dodecane and the additional solubility obtained by the addition of THF resulted in stable injection performance throughout the fluid test.

Figure 1 is a graph of Sr{ ^t BuC(O)CHC(NCH ₂ CH ₂ NMe ₂ )Me} ₂ (solid line) and Ti{MeC(O)CHC(NCH ₂ CH ₂ O)Me} ₂ (dotted line) Thermogravimetric analysis/differential scanning calorimetry (TGA/DSC) maps indicate that the two complexes are compatible due to very similar evaporation behavior.

Figure 2 is Sr{ ^t BuC(O)CHC(NCH(Me)CH ₂ NMe ₂ )Me} ₂ (solid line) and Ti(MeC(O)CHC(NCH(Me)CH ₂ O)Me) ₂ (point The TGA/DSC pattern of the underlined shows that the two complexes show compatibility due to the same melting point and similar evaporation lines.

3 is a graph showing the temperature relationship of PEALD when SrO is deposited by using Sr{ ^t BuC(O)CHC(NCH ₂ CH ₂ NMe ₂ )Me} ₂ and O ₂ plasma.

Figure 4 is a graph showing the relationship between the thickness of SrO obtained by PEALD at a temperature of 250 ° C and the number of deposition cycles using Sr{ ^t BuC(O)CHC(NCH ₂ CH ₂ NMe ₂ )Me} ₂ and O ₂ plasma. .

Figure 5 shows the relationship between the thickness of SrO obtained and the Sr precursor -Sr{ ^t BuC(O)CHC(NCH ₂ CH ₂ NMe ₂ )Me} ₂ pulse time when PEALD was carried out at 250 °C.

Figure 6 is a graph showing the temperature dependence of thermal ALD when Sr{ ^t BuC(O)CHC(NCH ₂ CH ₂ NMe ₂ )Me} ₂ and ozone are used to deposit SrO.

Figure 7 is a graph showing the temperature dependence of thermal ALD when Sr{ ^t BuC(O)CHC(NCH(Me)CH ₂ NMe ₂ )Me} ₂ and ozone are used to deposit SrO.

Figure 8 shows the direct liquid ejection stability as demonstrated by back pressure monitoring prior to injection of the orifice. b) 0.1M 锶 precursor - Sr{ ^t BuC(O)CHC(NCH(Me)CH ₂ NMe ₂ )Me} _{2 when} dissolved in 1,3,5-trimethylbenzene; a) 0.1M锶The precursor -Sr{ ^t BuC(O)CHC(NCH(Me)CH ₂ NMe ₂ )Me} _{2 was} dissolved in 10% by weight of tetrahydrofuran in dodecane.

Claims (31)

A cyclic deposition method for forming a ternary metal oxide film, wherein a plurality of precursors are sequentially introduced into a deposition chamber, evaporated, and deposited on a substrate under conditions for forming the ternary metal oxide film, which is improved The method comprises: using a first metal ketimine salt as a first precursor; using an oxygen source; using a second metal ketimine salt as a second precursor different from the former; and utilizing an oxygen source, wherein One of the first or second metal ketimine salts is selected from the group consisting of the following structure A: Wherein M is a Group 2 divalent metal selected from the group consisting of calcium, magnesium, strontium and barium; wherein R ^{1 is} selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, an alicyclic group, and a group consisting of aryl groups having 6 to 12 carbon atoms; R ^{2 is} selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alicyclic group, and an aryl group having 6 to 12 carbon atoms. a group consisting of; R ^{3 is} selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, an alicyclic group, and an aryl group having 6 to 12 carbon atoms; R ⁴ is with or without a C _2-3 linear or branched alkylene bridge having a palmitic carbon atom, thereby forming a five- or six-membered coordination ring with a metal center; R ^5-6 independently selected from having from 1 to 10 a group consisting of an alkyl group of a carbon atom, a fluoroalkyl group, an alicyclic group, and an aryl group having 6 to 12 carbon atoms, and they are capable of linking to form a ring containing a carbon, oxygen or nitrogen atom; and the first one or The other of the second metal ketimine salts is selected from the group consisting of the following structure B: Wherein M is a tetravalent metal selected from the group consisting of titanium, zirconium and hafnium; wherein R ^{7 is} selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, an alicyclic group, and having 6 to 12 a group consisting of aryl groups of carbon atoms; R ^{8-9 is} selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alicyclic group, and an aryl group having 6 to 12 carbon atoms. R ¹⁰ is a C _2-3 linear or branched alkylene bridge with or without a palmitic carbon atom, thereby forming a five- or six-membered coordination ring with the metal center. The method of claim 1, wherein the metal ketimine is delivered via direct liquid transport by dissolving a metal ketimine salt in a solvent or solvent mixture to prepare a solution having a molar concentration of 0.01-2 M. salt. The method of claim 2, wherein the solvent is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, linear or cyclic ethers, esters, nitriles, alcohols, amines, polyamines, organic guanamines, and mixtures thereof. . The method of claim 3, wherein the solvent is selected from the group consisting of tetrahydrofuran (THF), 1,3,5-trimethylbenzene, dodecane, N-methylpyrrolidone (NMP), and mixtures thereof. group. The method of claim 1, wherein the metal oxide is barium titanate. The method of claim 1, wherein the cyclic deposition method is a cyclic chemical vapor deposition method. The method of claim 1, wherein the cyclic deposition method is an atomic layer deposition method. The method of claim 1, wherein the deposition chamber is The pressure is 50 mTorr to 100 Torr and the temperature in the deposition chamber is below 500 °C. The method of claim 1, wherein the oxygen-containing source is selected from the group consisting of oxygen, oxygen plasma, water, water plasma, ozone, nitrous oxide, and mixtures thereof. The method of claim 1, wherein the obtained ternary metal oxide film is subjected to rapid thermal annealing or plasma treatment to densify the obtained ternary metal oxide film. The method of claim 1, wherein the metal ketimine salt of structure A is selected from the group consisting of Sr{ ^t BuC(O)CHC(NCH ₂ CH ₂ NMe ₂ )Me} ₂ , Sr{ ^t BuC(O CHC(NCH ₂ CH ₂ NEt ₂ )Me} ₂ ,Sr{ ^t BuC(O)CHC(NCH(Me)CH ₂ NMe ₂ )Me} ₂ and Sr{ ^t BuC(O)CHC(NCH(Me)CH ₂ NEt ₂ )Me} ₂ group; the metal ketone imide salt of structure B is selected from Ti{MeC(O)CHC(NCH ₂ CH ₂ O)Me} ₂ and Ti(MeC(O)CHC(NCH(Me) a group consisting of CH ₂ O)Me) ₂ . A cyclic deposition method for forming a multi-component metal oxide film, wherein a plurality of precursors are introduced into a deposition chamber, evaporated, and deposited on a substrate under conditions in which the multi-component metal oxide film is formed, and the improvement thereof The method comprises: dissolving at least two metal ketimine salts in a solvent or a solvent mixture to prepare a solution; and utilizing an oxygen-containing source, wherein the at least two metal ketimine salts comprise a metal ketone represented by structure A The imine salt and another metal ketimine salt represented by structure B each have a molar concentration of 0.01-2 M; wherein the definitions of structures A and B are as follows: Wherein M is a Group 2 divalent metal selected from the group consisting of calcium, magnesium, strontium and barium; wherein R ^{1 is} selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, an alicyclic group, and a group consisting of aryl groups having 6 to 12 carbon atoms; R ^{2 is} selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alicyclic group, and an aryl group having 6 to 12 carbon atoms. a group consisting of; R ^{3 is} selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, an alicyclic group, and an aryl group having 6 to 12 carbon atoms; R ⁴ is with or without a C _2-3 linear or branched alkylene bridge having a palmitic carbon atom, thereby forming a five- or six-membered coordination ring with a metal center; R ^5-6 independently selected from having from 1 to 10 a group consisting of an alkyl group of a carbon atom, a fluoroalkyl group, an alicyclic group, and an aryl group having 6 to 12 carbon atoms, and they are capable of linking to form a ring containing a carbon, oxygen or nitrogen atom; Wherein M is a tetravalent metal selected from the group consisting of titanium, zirconium and hafnium; wherein R ^{7 is} selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, an alicyclic group, and having 6 to 12 a group consisting of aryl groups of carbon atoms; R ^{8-9 is} selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alicyclic group, and an aryl group having 6 to 12 carbon atoms. R ¹⁰ is a C _2-3 linear or branched alkylene bridge with or without a palmitic carbon atom, thereby forming a five- or six-membered coordination ring with the metal center. The method of claim 12, wherein the solution of the metal ketimine salt is delivered by direct liquid injection. The method of claim 12, wherein the solvent is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, linear or cyclic ethers, esters, nitriles, alcohols, amines, A group consisting of a polyamine, an organic guanamine, and a mixture thereof. The method of claim 14, wherein the solvent is selected from the group consisting of tetrahydrofuran (THF), 1,3,5-trimethylbenzene, dodecane, N-methylpyrrolidone (NMP), and mixtures thereof. group. The method of claim 12, wherein the multi-component metal oxide is barium titanate. The method of claim 12, wherein the cyclic deposition method is a cyclic chemical vapor deposition method. The method of claim 12, wherein the metal ketimine salt of structure A is selected from the group consisting of Sr{ ^t BuC(O)CHC(NCH ₂ CH ₂ NMe ₂ )Me} ₂ , Sr{ ^t BuC(O CHC(NCH ₂ CH ₂ NEt ₂ )Me} ₂ ,Sr{ ^t BuC(O)CHC(NCH(Me)CH ₂ NMe ₂ )Me} ₂ and Sr{ ^t BuC(O)CHC(NCH(Me)CH ₂ NEt ₂ )Me} ₂ group. The method of claim 12, wherein the metal ketimine salt of structure B is selected from the group consisting of Ti{MeC(O)CHC(NCH ₂ CH ₂ O)Me} ₂ and Ti{MeC(O)CHC ( A group consisting of NCH(Me)CH ₂ O)Me} ₂ . The method of claim 1, wherein R ^{1 is} selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, and an alicyclic group. The method of claim 1, wherein R ^{2 is} selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, and an alicyclic group. The method of claim 1, wherein R ^{3 is} selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, and an alicyclic group. The method of claim 1, wherein R ^{5-6 is} selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, and an alicyclic group. The method of claim 1, wherein R ^{7 is} selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, and an alicyclic group. The method of claim 1, wherein R ^{8-9 is} selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, and an alicyclic group. The method of claim 12, wherein R ^{1 is} selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, and an alicyclic group. The method of claim 12, wherein R ^{2 is} selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, and an alicyclic group. The method of claim 12, wherein R ^{3 is} selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, and an alicyclic group. The method of claim 12, wherein R ^{5-6 is} selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, and an alicyclic group. The method of claim 12, wherein R ^{7 is} selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, and an alicyclic group. The method of claim 12, wherein R ^{8-9 is} selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, and an alicyclic group.